JPH0335051A - Polycarbonate mixture - Google Patents

Abstract

PURPOSE: To obtain a polycarbonate mixture constituted of a specific thermoplastic aromatic polycarbonate resin, a thermoplastic polycarbonate resin other than this and an additive for an optical use added at any time and useful for producing a compact disk.

CONSTITUTION: A polycarbonate mixture consists of 0.1-99.9 wt.% thermoplastic aromatic polycarbonate with a wt. average mol.wt. of 10,000 or more (A) consisting of 100-2 mol% of a difunctional carbonate structural unit represented by formula I (wherein R¹ and R² are each H, a halogen, a 1-3C alkyl or a 5-6C cycloalkyl, (m) is 4-7, R³ and R⁴ selected with respect to groups X are independently H or a 1-6C alkyl, X is a carbon atom and R³ and R⁴ are each an alkyl at least one of which is on one X-atom) and the remainder of a difunctional carbonate structural unit represented by formula II (wherein Z is a 6-30C aromatic group), 99.9-0.1 wt.% of thermoplastic polycarbonate (B) other than A containing only the structural unit represented by formula II and an additive (C) for an optical use added at any time.

COPYRIGHT: (C)1991,JPO

Description

[Detailed description of the invention]

German patent application no. P3,833,953.6 (Le
A 26,397) relates to mixtures of a) certain novel polycarbonates and b) component a) special novel elastomers or thermoplastics other than polycarbonates and optionally C) customary additives, and processes for the production of these mixtures. German patent application No. P3,833,953.6 is known in the present application as follows: a) General formula (I) in which R' and R1 are independently hydrogen, /\logen, CI
” Cs alkyl, CS or C, cycloalkyl,
C6~C4・aryl or C7~C2! represents aralkyl; m represents an integer from 4 to 7; R3 and R4, which can be selected individually for each X, independently represent hydrogen or C1-C, alkyl; and X represents carbon: R3 and R4 together represent alkyl on at least one atom of The present invention relates to a mixture containing an agent, and a method for producing the same. German patent application p3.832,396.6 (Le
A 26.344) describes the polycarbonate (a) of the mixture according to the invention and its starting materials as well as its preparation. The starting material for polycarbonate (a) is dihydroxydiphenylcyclohexane (I)1, where R1 and HR are independently hydrogen, halogen, preferably chlorine or bromine, CI-C, alkyl, C1 or C, cycloalkyl, C1- C, aryl, preferably phenyl and C2-C, aralkyl, preferably phenyl-C+ "" Ca alkyl, especially benzyl; m represents an integer from 4 to 7, preferably 4 or 5; R3 and R1, which may be selected individually, independently represent hydrogen or C1-C, alkyl; and X represents carbon; with the proviso that Rs and R6 together represent alkyl on at least one X atom; It is. R3 and R4 preferably both have 1 or 2 X atoms,
In particular it represents alkyl on only one X atom. Methyl is the preferred alkyl group and the
Alkyl substitution in the - position is preferred. Dihydroxydiphenylcyclohexane (general formula (in which m represents 4 or 5) having 5 or 6 ring carbon atoms in the cycloaliphatic group, for example diphenol, is preferred, 1.1-bis-(4-hydroxyphenyl )-3,3,5-trimethylcyclohexane (I[) is particularly preferred. Dihydroxydiphenylcycloalkane (I) can be produced by condensing phenol (V) in a known manner; 1 and ketone (■) : In the formula, X, R', R'', R3, R4 and m represent the general formula (1
) is defined in relation to Phenol (V) is known in the literature or can be obtained by methods known in the literature [e.g. cresol and xylenol,
s Encyclopadie der techni
schenChemie), 4th and expanded edition, No. 15
Volume, pp. 61-77, Verlag Hemi
Chemie) - Finnheim New York 197
8; Chlorophenol, Ullmans, Engineering Cyclopedi, 1st 4th edition, Verlag Hemie, 1975; Volume 9, pp. 573-582; and Hyalkylphenol, Ullmans, Engineering See Der Technitzchen Hemy - 4th edition, Verlag Hemy - 1979; Vol. 15, pp. 191-214]. Examples of phenol (V) include phenol, 0-
Cresol, m-cresol, 2,6-dimethylphenol, 2-chlorophenol, 3-chlorophenol,
2.6-'; There are chlorophenol, 2-cyclohexylphenol, phenylphenol and 0-benzylphenol. Ketones (Vl) are known in the literature

[For example, Beilsteins Handbook der Organischen ◆ Hemy (Beilsteins Handbuck der
Organischen Chamois, Volume 7, 4th Edition, Springer Verlag
-Verlag), Berlin, 1925 and corresponding augmentations 1-4, and J, A+s. Chew, Soc, Volume 79 (1957), 1488
~1492 pages, U.S. Patent No. 2.629.289, Allan et al., J. Chew, Soc.
, (1959), 2186-2192 and J.O.
rg, Chew, Volume 38, (1973), 4431
〜4435 pages, J. Arm, ,Cbe+m-Soc, 8U, (19
65), pp. 1353-1364]. Ketone (Vl)
For example, a general method for producing ``Organicum''
kuw+), 15th edition, 1977, vEB-Deutscher Verlag der Bissemschaften (Deutsc
Her Verlag der Wisse+5sch
aften), Berlin, p. 698, for example. Examples of known ketones (Vl) include: 3.3
-dimethylcyclopentanone, 3,3-dimethylcyclohexanone, 4,4-dimethylcyclohexanone, 3-
Ethyl-3-methylcyclopene9/n, 2,3.3-trimethylcyclopentanone, 3.3.4-trimethylcyclopentanone, 3.3-dimethylcycloheptanone,
4.4-dimethylcyclohebutanone, 3-ethyl-3-
Methylcyclohexanone, 4-ethyl-4-methylcyclohexanone, 2.3.3-trimethylcyclohexanone, 2,4.4-trimethylcyclohexanone, 3゜3
．． 4-) Dimethylcyclohexanone, 3,3.5-trimethylcyclohexanone, 3.3.4-1-dimethylcyclohexanone, 3.3.5-trimethylcycloheptanone, 3.5.5-trimethylcycloheptanone, 5-
Ethyl-2,5-dimethylcycloheptanone, 2.3.
3.5-tetramethylcycloheptanone, 3.3.5.
5-tetramethylcycloheptanone, 4-ethyl-2,
3,4-)limethylcyclobentanone, 3-ethyl-4
-isopropyl-3-methylcyclopentanone, 4-5
ec-butyl-3,3-dimethylcyclopentanone, 2
-isopropyl-3,3,4-trimethylcyclopentanone, 3-ethyl-4-isopropyl-3-methylcyclohexanone, 4-ethyl-3-isopropyl-4-methylcyclohexanone, 3-sec-butyl-4,4-
Dimethylcyclohexanone, 2-butyl-3,3,4-
) dimethylcyclopentanone, 2-butyl-3,3,4
-) dimethylcyclohexanone, 4-butyl-3,3,
5-1-dimethylcyclohexanone, 3-isohexyl-3-methylcyclohexanone, 2,2-dimethylcyclooctanone and 3.3.8-1-dimethylcyclooctanone. Suitable ketones include; υ To produce bisphenols, ketones (Vl
) 2 to 10 mol, preferably 2.5 to 6 mol, of phenol (V) are used per mol. The preferred reaction time is l-
It is 100 hours. Generally, the reaction is carried out at -30 to 300°C.
Preferably a temperature of -15 to 150°C and a temperature of l to 20/(-
preferably 1. - Perform at a pressure of 10 bar. Generally, the reaction is carried out in the presence of an acid catalyst. Examples include hydrogen chloride, hydrogen bromide, hydrogen fluoride, boron trifluoride, aluminum trichloride, zinc dichloride, titanium tetrachloride, tin tetrachloride,
There are phosphorus halides, phosphorus pentoxide, phosphoric acid, concentrated hydrochloric acid or sulfuric acid, and mixtures of acetic acid and acetic anhydride. It is also possible to use acid ion exchangers. Furthermore, the reaction is preferably carried out using cocatalysts such as C1-CtS alkyl mercaptans, hydrogen sulfide, thiophenols, thio acids in an amount of 0.01 to 0.4 mol 1 mol ketone, more preferably 0.05 to 0.2 mol 1 mol ketone. and can be accelerated by adding dialkyl sulfides. The condensation may be carried out without a solvent or in the presence of an inert solvent (eg aliphatic and aromatic hydrocarbons or chlorohydrocarbons). If the catalyst simultaneously acts as a water scavenger, there is no need to add an additional water scavenger, although the latter is advantageous in order to obtain good conversions in each case where the catalyst used does not combine with the water resulting from the reaction. . Suitable water removing agents include, for example, acetic anhydride, zeolites, polyphosphoric acid and phosphorus pentoxide. Phenol (V) and ketone (Vl) Ha2: l~
10:l, preferably 2.5:l to 6:HF
) (V): (■) molar ratio, -30 to 300°C,
The reaction is preferably carried out at a temperature of -15 to 150° C. and a pressure of 1 to 20 bar, preferably 1 to 10 bar, in the presence of an acid catalyst and optionally a cocatalyst and/or solvent and/or water removing agent. obtain. In the general formula (I), R3 and R6 are preferred and s< together represent alkyl on 1 or 2 X atoms, in particular on only one X atom, methyl is a preferred alkyl group;
Ethyl or C3 which can be linear or branched
C, alkyl groups may also be used. a- for diphenyl-substituted carbon atom (C-1)
The X atom in position is preferably not dialkyl-substituted, whereas disubstitution with alkyl in the β-position relative to C-1 is preferred. In some cases, the reaction does not proceed homogeneously, ie several different products may be formed, so the desired compound must first be removed from the mixture. For details on condensation, see Schnell (5chne 11), Chemistry and of Polycarbonates.
Physics of Polycarbonates
), Interscience Publishing, New York 1964. In some cases, the reaction can be controlled by selecting the appropriate catalyst and reaction conditions so that the desired compound precipitates or crystallizes out and is thereby removed. The following example illustrates the preparation of diphenol (II). Example A 7.5 mol of phenol (7052) and 0.15 mol of dodecylthiol (30,35 ml) were placed in a 1Q round bottom flask equipped with a stirrer, a dropping funnel, a thermometer, a reflux condenser and a gas inlet. and the mixture was saturated with dry HCQ gas at a temperature of 28-30 °C. dihydroisophorone (3,3,5-trimethylcyclohexan-1-one).
1.5 moles (2102) and 1.5 moles (1
A solution of 512) was added dropwise to this solution over a period of 3 hours, while HCO gas was also fed through the reaction solution. When the reaction was complete, HCQ gas was introduced for an additional 5 hours. The reaction continued for 8 hours at room temperature. Excess phenol was then removed by steam distillation. The remaining residue was extracted hot twice with petroleum ether (60-90) and once with methylene chloride and removed by filtration. Yield: 370j Melting point: 205-207°C Polycarbonate (a) is German patent application No. P3.8
32,396.6 from diphenol (1). Diphenols (1) to form homopolycarbonates and several diphenols (1) to form copolycarbonates can be used together. (1) may be used in a mixture with other diphenols such as formula 10-Z-OH (■). Other suitable diphenols HO-Z-OH (■) are 2 to 1
Carbon atoms containing one or more aromatic rings, which are substituted and which may contain aliphatic or cycloaliphatic groups other than those corresponding to general formula (I), or heteroatoms as bridging members. It represents an aromatic group having 6 to 30 atoms. Examples of diphenols (■) include: hydroquinone, resorcinol diphenyl, bis-(hydroxyphenyl)-alkane, bis-(hydroxyphenyl)-cycloalkane, bis-(hydroxyphenyl)-sulfide, bis- (hydroxyphenyl)-ether, bis-(hydroxyphenyl)-ketone, bis-(hydroxyphenyl)-sulfone, bis-(hydroxyphenyl)-sulfoxide, (1,t'-bis-(hydroxyphenyl)-diisopropylbenzene and its Ring-alkylated and ring-halogenated derivatives. These and further suitable diphenols are described, for example, in U.S. Pat. No. 3.028.365; Issue: No. 3
．． 275.601: 2.991.273; 3.271.367; 3.062.781: 2.970.131: and 2. 999, 846: German Patent Application Publication No. 1.57
0, 70 No. 3: Same No. 2.063.050; Same No. 2, 063.052; Same No. 2.211.0956;
French Patent No. 1.561.518; and “H.
Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishing, New York 1964. Other suitable diphenols include, for example, 4,4'-dihydroxydiphenyl, 2,2-bis-(4-hydroxyphenyl)-propane, 2,4-t'-(4-hydroxyphenyl)-2- Methylbutane, l. ! -bis-(4-hydroxyphenyl)-cyclohexane, a,a-bis-(4-hydroxyphenyl)-
p-'; isoglobilbenzene, 2,2-bis-(3-
Methyl-4-hydroxyphenyl)-propane, 2.2
-Bis-(3-chloro-4-hydroxyphenyl)-propane, bis-(3.5-dimethyl-4-hydroxyphenyl)-methane, 2
．． 2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfone, 2,4-bis-(3,
5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1ll-bis-(3,5-dimethyl-4-hydroxyphenyl)-cyclohexane, α,/-bis-
(3,5-dimethyl-4-hydroxyphenyl)-p-
Diisoglopylbenzene, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-furopane and 2.
There is 2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane. Examples of particularly suitable diphenols (■) are: 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dimethyl-4-hydroxy phenyl)-propane, 2°2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane, 2.2
-bis-(3,5-sifukumo-4-and droxyphenyl)-propane and 1,1-bis-(4-hydroxyphenyl)-cyclohexane. 2.2-Bis-(4-hydroxyphenyl)-propane is particularly preferred. Other diphenols may be used individually and together as mixtures. The molar ratio of diphenol (I) to other diphenols used together, such as those corresponding to general formula (■), is (
I) 100 mol%: 98 mol% of other diphenols, preferably (1) 100 mol%: 98 mol% of other diphenols, especially (I) 100 mol%: other diphenols 0 mol%: 90 mol% of other diphenols, very especially (1) 1
00 mo%: 0 mole% of other diphenols (1) 20 mole%:
Other diphenols should be 80 mol%. Diphenols, optionally in combination with other diphenols (1
) can be produced by known polycarbonate production methods. Various diphenols can thus be linked to each other randomly or in blocks. Polycarbonates may be branched by known methods. If branching is necessary, a small amount, preferably 0.05 to 2.0 mol % (based on the diphenol used), of at least trifunctional compounds, in particular 3 or more phenols, can be added in a known manner. This can be achieved by condensing substances with a specific hydroxyl group. Fractalizing agents having three or more phenolic hydroxyl groups include: chloroglucinol, 4,6-dimethyl-2. 4,61 Lee(4-hydroxyphenyl)-hept-2
-ene, 4,6-dimethyl-2,4,6-tri(4-
hydroxyphenyl)-hebutane, 1,3.5-)ly(4-hydroxyphenyl)-benzene, 1.1.1-
) li-(hydroxyphenyl)-ethane, tri(4-
hydroxyphenyl)-phenylmethane, 2,2-bis-[4,4-bis(4-hydroxyphenyl)-cyclohexyl]-propane, 2,4-bis-(4-hydroxyphenylisopropyl)-phenol, 2.6-bis (2-hydroxy-5'-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-
(2.4-dihydroxyphenyl)-furopane, hexa-[4-(4-hydroxyphenylisopropyl)-7
22ylj-ortho-terephthalate, tetra-(4-hydroxy7enyl)-methane, tetra-[4-(4-hydroxyphenylisopropyl)-phenoxy, cy]-methane and 1,4-bis-[ (4'.4"-dihydroxytriphenyl)-methylbutanzene. Some other trifunctional compounds include 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3.
3-bis-(3-methyl-4-hydroxyphenyl)-
There is 2-oxo-2,3-dihydroindole. Customary concentrations of trifunctional compounds are used as chain terminators to adjust the molecular weight of polycarbonate (a) in a known manner. Suitable compounds include, for example, phenol, t-butylphenol or other C1-C, alkyl-substituted phenols. A small amount of phenol (■) in the formula to adjust the molecular weight,
R represents a branched chain Ca and/or C, an alkyl group, is particularly suitable. The ratio of CH and protons in the alkyl group R is preferably 47 to 89%, and
The ratio of H, proton is preferably 53 to 11%; and R is preferably 〇- and/or p- to OH group.
The upper limit of the ortho ratio is particularly preferably 2.
It is 0%. The chain terminator is 0.5 to 10% by mole, preferably 1.5 to 8% by mole based on the commonly used diphenol.
Use in the amount of Polycarbonate (a) may preferably be produced by a known method by the phase interface method (see H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Review, Vol. . In this method the diphenol (I) is dissolved in the aqueous alkaline phase. For the preparation of copolycarbonates with other diphenols, mixtures of liphenol (I) and other diphenols, such as those corresponding to the general formula (■), are used. For example, a chain terminator corresponding to general formula (■) can be added to adjust the molecular weight. The mixture is then reacted with phosgene by a phase interfacial polymerization process, preferably in the presence of an inert organic phase which dissolves the polycarbonate. The reaction temperature is 0 to 40"O. Used together as needed (preferably 0.05 to 2.0 mol%)
The branching agent can be added either with the diphenol in the aqueous alkaline phase or dissolved in an organic solvent before reacting with phosgene. In addition to Schiffle (1), its monochlorocarbonate and/or bischlorocarbonate can also be used, these being added dissolved in an organic solvent. The amount of chain terminator and branching agent then depends on the molar amount I of diphenol groups (1) and optionally (■); if chlorocarbonate is co-used, the amount of phosgene is reduced according to known methods. obtain. Suitable organic solvents for the chain terminator and optionally branching agent and the chlorocarbonate include, for example, methylene chloride, chlorobenzene, acetone, acetonitrile and mixtures of these solvents, especially methylene chloride and chlorobenzene. The chain terminators and branching agents used can optionally be dissolved in similar solvents. Examples of organic phases for phase interfacial polymerization include methylene chloride, chlorobenzene and mixtures of methylene chloride and chlorobenzene. Aqueous NaOH is an example of an aqueous alkaline phase. The preparation of polycarbonate (a) by the phase interface process can be catalyzed in conventional manner with catalysts such as tertiary amines, in particular tertiary aliphatic amines such as tributylamine or triethylamine; the catalyst depends on the number of moles of diphenol used. Amounts of 0.05 to 10 mol % can be used as a basis. The catalyst may be added before, during or after the start of the phosgenation. Polycarbonate (a) can also be prepared by known methods in homogeneous phase, the so-called "pyridine method" and the known melt transesterification method, for example using diphenyl carbonate instead of phosgene. Polycarbonate (a) is compatible with applications in the injection molding industry and preferably has a molecular weight of at least 10,000, particularly preferably from 10,000 to 300,000, especially 4:20,0
00 to 80.000 (73 molecular weight FJi W (weight average, determined by gel chromatography after previous calibration). These can be linear or branched and contain diphenols (1 ).The polycarbonates according to the invention are thus homopolycarbonates or copolycarbonates based on polycarbonate containing 1 difunctional carbonate structural unit in each case
Difunctional carbonate structural units (1a) in an amount of from 100 to 2 mol %, preferably from 100 to 5 mol %, in particular from 100 to 10 mol %, very especially from 100 to 20 mol %, based on the total amount of 00 mol %. In the formula, X, R", R", 11% R4 and m are represented by the general formula (I
) defined in relation to at least 10,000, preferably 10°00
0~200,000. Especially 20.000~80°000
It is a high molecular weight, thermoplastic aromatic polycarbonate with FJiW (weight average molecular weight) of . Thus, the polycarbonate, for example, totals 100 mol%
up to 0 to 98 mol %, preferably 0 to 95 mol %, in particular 0 to 90 mol %, very particularly Preferably 0 to 80 mol%
Contains other difunctional carbonate structural units corresponding to the general formula ().

[-2- in general formula (■a) corresponds to -2- in general formula (■)] By blending 1 diphenol (I), a new polycarbonate with high heat resistance and other good properties was created. is rawhide. This applies in particular to diphenols (I) in which m is 4 or 5, and very particularly to diphenols (I) in which m is 4 or 5.
Ib) This is true for polycarbonates based on Ib) in which R1 and R1 are independently defined in relation to general formula (I) and particularly preferably represent hydrogen. Preferred polycarbonate (a) is m is a structural unit (Ia)
and very especially the unit (Ic) in which R1 and R1 are defined with respect to the general formula (Ia), but are particularly preferably hydrogen. Diphenols (Ib) in which R1 and R1 in particular represent hydrogen
In addition to their high heat resistance, polycarbonates based on . In addition, the polycarbonate properties can be suitably varied by selecting the composition with other diphenols, in particular those corresponding to the general formula (■). In the following Examples 8.1-8.5 the preparation of polycarbonate (a) is described. Relative viscosities are measured against 0.5% by weight polycarbonate solutions in CH,CQ. Freezing temperature or glass transition temperature is determined by differential scanning calorimetry (D
Measured by SC). Example 8. 1 Diphenol (n) 31.02 (0.1 mol), xon
33. 1 (0.6 mol) and 560 I of water were dissolved under an inert gas atmosphere with stirring. Next, phenol 0.1881 in methylene chloride 560
A solution of was added. 19.87 (0°2 moles) of phosgene were introduced into a well-stirred solution at pH 13-14 and 21-25°C. Then 0.1 ml of ethylpiperidine was added and the solution was stirred for a further 45 minutes. After separating off the bisphenolate-free aqueous phase and partially acidifying it with phosphoric acid, the organic phase was washed with water until neutral and the solvent was removed. The polycarbonate exhibited a relative viscosity of 1.259. The glass transition temperature of the polymer was measured as 233°C (DSC). Example 8.2 Bisphenol A [2,2-bis-(4-hydroxyphenyl)-propane] 68.41 (0.3 mol)
, diphenol (II) 217. Oj (0.7 mol), KOH 336.61 (6 mol) and 2700 g of water were dissolved under an inert gas atmosphere with stirring. Next, 2.500ml of methylene chloride! A solution of 1.889% of phenol in water was added. Phosgene 1982 (2 mol) at pH 1
The mixture was introduced into a well-stirred solution at 3-14 and 21-25°C. Ethylpiperidine l- was then added and the solution was stirred for an additional 45 minutes. After separation of the bisferrate-free aqueous phase and partial acidification with phosphoric acid, the organic pores were washed with water until neutral and the solvent was removed. The polycarbonate exhibited a relative viscosity of 1.336. The glass transition temperature of the polymer was measured as 212°C (D SC). Example 8.3 A mixture of bisphenol A l l 42 (0.5 mol) and diphenol (n)l 552 (0.5 mol) was reacted as in Example 8.2 to form a polycarbonate. The polycarbonate exhibited a relative viscosity of 1.386. The glass transition temperature of the polymer was measured as 195°C (DSC). Example 8.4 A mixture of bisphenol Al 59.67 (0.7%) and diphenol (II) 931 (0.3 mol) was reacted as in Example 8.2 to form a polycarbonate. The polycarbonate exhibited a relative viscosity of 1.437. The glass transition temperature of the polymer was determined as 180"O(DSC)'. Example 8.5 Diysno/L; (II) 31.01 (0.1 mol)
, NaOH24,0JJ (0-6 mol) and water 27o2
was dissolved under an inert gas atmosphere with stirring. A solution of 0.3091 of 4-(1,1,3,3-tetramethylbutyl)-phenol in 25 OseQ of methylene chloride was then added. Phosgene 19.87 (0.2 mol) p813
Ethylpiperidine 0IIlII2 was introduced into the well-stirred solution at ~14 and 21-25 °C, and the solution was stirred for a further 45 min. The bisphenol-free aqueous phase was separated off and partially treated with phosphoric acid. After acidification, the organic phase was washed with water until neutral and the solvent was removed. The polycarbonate exhibited a relative viscosity of 1.314. The glass transition temperature of the polymer was measured as 234°C (D SC). In order to estimate the UV resistance of polycarbonate, we investigated the main radical formation during UV irradiation with a mercury vapor lamp (Edgefilter 305n-) in polycarbonate based on 2,2-bis-(4-hydroxyphenyl)-globan. It was measured in comparison with. The polycarbonate of Example B, 1 was shown to have a low primary radical formation rate and therefore high resistance to ultraviolet light. The object of the invention of German patent application no.
00 to 5 mol %, in particular 100 to 10 mol %, very in particular 100 to 20 mol % of difunctional carbonate structural units (
Summer a) In the formula, X, R1, R3, R1, R◆ and m represent the general formula (1
) at least to, ooo, preferably Io. 000~300,000. 0.1 to 99.9% by weight, preferably 1% by weight of thermoplastic aromatic polycarbonates of high molecular weight of 20.000 to 80.000 (F) Rw (weight average molecular weight), especially for applications in the field of injection IRM. ~98% by weight, in particular 2.5-90% by weight, and b) 99.9-99.9% by weight, preferably 99-2% by weight of elastomers or thermoplastics other than polycarbonates of a), in particular 97.5 to 10% by weight,
In that case, the sum of a) + b) is 100% by weight in each case.
is a mixture. Particularly suitable polycarbonates (a) have structural units (Ia)
in which m represents 4 or 5, and very particularly the structural unit (Ic) in which R' and R1 are as defined in relation to the general formula (Ia) but particularly preferably represent hydrogen. It is something. Other thermoplastics suitable as component (b) in the mixtures of the invention are bl) amorphous thermoplastics, preferably above 40°C;
In particular, both those having a glass transition temperature of 60 DEG to 220 DEG C. and b2) partially crystalline thermoplastics, preferably having a melting temperature of 60 DEG C. or higher, in particular 80 DEG to 400 DEG C. The elastomer for component b) of the mixture according to the invention is b3) below 0°C, preferably below -10°C, especially below -1°C.
It is a polymer with a glass transition temperature of 5 to -140°C. Examples of other amorphous thermoplastics bl) include polycarbonates, polyamides, polyolefins, polysulfones, polyketones, thermoplastic vinyl polymers such as polymethacrylates or homopolymers of vinyl aromatic compounds, copolymers of vinyl aromatic compounds or Non-grade polymers are selected from graft polymers of vinyl monomers on rubber, polyethers, polyimides and thermoplastic polyurethanes. Examples of crystalline thermoplastics b2) include aliphatic polyesters, polyarylene sulfides and partially crystalline representatives of the thermoplastics included in bl) above. Examples of elastomers b3) include a wide range of rubbers, such as ethylene-propylene rubber, polyisoprene, polychloroprene, polysiloxane, active polypropylene, diene rubbers, olefin rubbers, acrylate rubbers and natural rubbers, styrene-butadiene block copolymers, There are copolymers of ethylene and vinyl acetate or (meth)acrylates, elastic polyurethanes which are not thermoplastics, including bl) or b2), and elastic polycarbonate-polyether block copolymers. Amorphous thermoplastic bl) is a German patent application no.
．． 832,396.6 (LeA 26.344), especially polycarbonates. These other polycarbonates are both homocarbonates and polycarbonates, both of which can be linear or branched. Particularly preferred bisphenol A [-2,2-bis-(4-hydroxyphenyl)-
It's propane J. These other thermoplastic polycarbonates are known. The molecular weight MY (weight average molecular weight, measured by gel permeation chromatography in tetrahydro 7 run) of other thermoplastic polycarbonates is 10.000 to 300,000.
Preferably it is 12,000 to 15o, ooo. Other thermoplastic polycarbonates can be used alone or in admixture with one another for component b) of the mixture according to the invention. Other thermoplastics suitable as component b) for the preparation of the mixtures according to the invention are also aliphatic, thermoplastic polyesters, particularly preferably polyalkylene terephthalates, thus e.g. ethylene glycol, 1,3-propanediol, 1 .4-butanediol, 1,6-hexanediol and 1,4-bis-hydroxymethylcyclohexane. The molecular weight (MW
) is IO,000 to 80,000. Polyalkylene terephthalates can be obtained by known methods, for example by transesterification from dialkyl terephthalates and the corresponding diols (for example, U.S. Pat. No. 2,647.885; U.S. Pat. No. 2,643.989; U.S. Pat. No. 2,534 No. .028; No. 2.578.660
No. 2,742.494 and No. 2,901,4
(See No. 66). These polyesters are known. Furthermore, other suitable thermoplastics are thermoplastic polyamides. All crystalline polyamides are suitable, especially polyamide 6, polyamide 6.6 and partially crystalline copolyamides based on both of these components. The acid component may also be in particular wholly or partially adipic acid or caprolactam, terephthalic acid and/or isophthalic acid and/or
or speric acid and/or sebacic acid and/or azelaic acid and/or dodecanedicarboxylic acid and/or
or adipic acid and/or cyclohexane dicarboxylic acid, and the diamine component is wholly or partially in particular m-xylene diamine and/or p-xylene diamine and/or hexamethylene diamine and/or
or partially crystalline polyamides consisting of 2.2.4-trimethylhexamethylenediamine and/or 2.4-1-dimethylhexamethylenediamine and/or inphoronediamine are suitable and The compositions are known in principle from the art [e.g. Encyclopaedia of Polymers].
+aers), Volume 11, pp. 315 et seq.]. In addition, partially crystalline polyamides prepared wholly or partly from lactams having 6 to 12 carbon atoms can optionally be co-used with one or more of the starting materials I mentioned above. Are suitable. Particularly suitable partially crystalline polyamides are polyamide 6 and polyamide 6.6 or copolyamides with a low proportion of other co-components of up to about 10% by weight. Also suitable polyamides are, for example, diamines such as hexamethylene diamine, decamethylene diamine, 2.2.4-
Trimethylhexamethylenediamine or 2.4.4
-trimethylhexamethylene diamine, m-xylene diamine or p-xylene. diamine, bis-(4-aminocyclohexyl)-methane, 4,4'-diaminocyclohexylmethane and 2
．． 2'-diaminodicyclohexylmethane mixture, 2
．． 2-bis-(4-aminocyclohexyl)-propane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3-aminoethyl-3,3,5-)dimethylcyclohexylamine, 2,5-bis -(aminomethyl)-norbornane, 2,6-bis-(aminomethyl)-norbornane, l,4-diaminomethylcyclohexane and mixtures of these diamines with dicarboxylic acids such as oxalic acid, adipic acid, azelaic acid, decanedicarboxylic acid. acid, heptadecanedicarboxylic acid, 2.2.4-
) dimethyladipic acid, 2.4.4-) dimethyladipic acid, isophthalic acid and terephthalic acid, and non-grade polyamides obtained by polymerization with mixtures of these dicarboxylic acids. Thus, some of the above diamines and/or
Alternatively, non-grade copolyamides obtained by polymerization of dicarboxylic acids are included. Also included are amorphous copolyamides prepared with the co-use of ω-aminocarboxylic acids such as ω-aminocaproic acid, ω-aminoundecanoic acid or ω-aminolauric acid or lactams thereof. Particularly suitable non-grade thermoplastic polyamides are isophthalic acid, hexamethylene diamine and also diamines such as 4,4'-diaminodicyclohexylmethane, inphorone diamine, 2,2,4-trimethylhexamethylene diamine or 2, 4.4-trimethylhexamethylenediamine, 2.5-bis-(aminomethyl)-norbornane and/or 2.6-L's-aminomethyl)-
those obtainable from norbornane, those obtainable from in-7thalic acid, 4,4-diaminodicyclohexylmethane and ω-caglolactam, inphthalic acid, 3,3-dimethyl-4,4′-diaminodicyclohexylmethane and ω - from laurinlactam and from terephthalic acid and from 2,2,4-trimethylhexamethylenediamine and 2,4,4-)dimethylhexamethylenediamine. Also, instead of pure 4,4'-diaminodicyclohexylmethane, 70 to 99 mol% of 4,4'-diamino isomer, 0 to 30 mol% of 2,4'-diamino isomer, 0 to 99 mol% of 2,4'-diamino isomer,
A mixture of 2 mol % of the 2.2'-diamino isomer and optionally also the corresponding highly polymerized diamine obtained by hydration of technical diaminophenylmethane may be used. Suitable thermoplastic polyamides may also consist of a mixture of partially crystalline and non-crystalline polyamides, with the proportion of non-crystalline polyamide preferably being lower than the fraction of partially crystalline polyamide. In addition, non-grade polyamides and their production are known from the state of the art (for example, Ullmann, Encyclopédie der Technissien Hemi-1, Vol. 19;
50). Other suitable thermoplastics b) are also thermoplastic linear or branched polyarylene sulfides. These have a structural unit of the general formula, in which R1 to R4, which may be the same or different, represent C3 to C, alkyl, phenyl or hydrogen. Furthermore, the polyarylene sulfide may contain diphenyl units. Polyarylene sulfides and their production are known (
See for example US Patent No. 3.354,129 and European Patent Application No. 0.171.021). Other suitable thermoplastics b) include thermoplastic polyarylene sulfones. Suitable polyarylene sulfones have a range of 1.000 to 200.
000,f! L<1i have a weight average molecular weight Vlw (CHC (measured by light scattering in 2s) of 20.000 to 60°000. Examples of these include 20.000 to 20.000.
Weight average molecular weight of 000! 64.4'-dichlorodiphenylsulfone with gIw and polyarylenesulfones of bisphenols, especially 2°2-bis(4-hydroxyphenyl)propane, obtainable by known methods. These polyarylene sulfones are known (e.g. US Pat. No. 3,264,536, German Patent Application No. 1,794,171, British Patent No. 1,264.9).
00, U.S. Patent No. 3.641.207, European Patent Application No. 0.038.028, German Patent Application No. 3,601.419 and German Patent Application No. 3.601.420
(see issue). Suitable polyarylene sulfones may also be branched in known manner (for example, in German Patent Application No. 2
, 305.413). Other suitable thermoplastics b) are also thermoplastic polyphenylene oxides, preferably poly-(2°6-dialkyl-1,4-phenylene oxide). A suitable polyphenylene oxide of the present invention is 2.000-100.0
It has a weight average molecular weight of 111 (measured by light scattering method in chloroform) of 0.00, preferably 20°ooo to ao,ooo. These polyphenylene oxides are known. Suitable poly-(2,6-dialkyl-1,4-phenylene oxides) are prepared using oxygen in the presence of a catalytic combination of a copper salt and a tertiary amine in a known manner. They can be obtained by oxidative polymerization (see German Patent Application No. 2,126,434 and US Pat. No. 3,306,875). Particularly suitable poly-(2,6-dialkyl-1,4-7 dinilene oxides) are poly-[2,6-di(Ct~C1-
alkyl)-1,4-phenylene oxide J e.g. poly-(2,6-dimethyl-1,4-7 dinilene oxide)
It is. Other suitable thermoplastics b) are also aromatic polyetherketones (for example British Patent No. 1078.234).
No. 4,010,147 and European Patent Application No. 0,135,938). These are the repeating structural components -0-E-0-E', where -E'- represents a divalent group of bisaryl ketone; and -0-E-0- represents a divalent divalent group. represents a group, including. These compounds are disclosed, for example, in British Patent No. 1.078.234 by dialkali difert: alkali 〇-E-0.
-Alkali and bis-(halogenaryl)-ketones:
Haffi -E' -Haffi (here Ha
d represents halogen). Suitable dialkali diferts are, for example, those of 2,2-bis-(4-hydroxyphenyl)-propane;
The (halogenaryl)-ketone is 4,4'-dichlorobenzophenone. Other suitable thermoplastics b) are also thermoplastic vinyl polymers. The vinyl polymers relevant to this invention are vinyl compounds, copolymers of vinyl compounds and graft polymers of vinyl compounds on rubber. Suitable homopolymers and copolymers of the invention include styrene, σ
-C3 to C+z (cyclo)- of methylstyrene, acrylonitrile, methacrylatetrile, (meth)acrylic acid
Alkyl esters of vinyl cI-C4 carboxylates, copolymer mixtures being obtainable from mixtures of these vinyl compounds by known methods. Homogeneous polymers or copolymers have 0.3 to 1,5 dQ/
It should have a critical viscosity [Staudinger index 1] of 2 (measured in known manner in toluene at 23° C.). Suitable vinyl polymers include, for example, thermoplastic poly-C1-C
, alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, preferably methyl methacrylate, or ethyl methacrylate. These include both homopolymers and copolymers of these methacrylates. Furthermore, other ethylenically unsaturated copolymerizable monomers such as (meth)acrylonitrile, (
, -methyl)-styrene, bromostyrene, vinyl acetate, C1-C, alkyl acrylates, (meth)acrylic acid, ethylene, propylene and N-vinylpyrrolidone can be polymerized into the structure in low amounts. Suitable thermoplastic poly-C, -C,alkyl methacrylates according to the invention are known in the literature or can be obtained by methods known in the literature. Suitable polymers are also styrene or copolymers of a-methylstyrene and acrylonitrile, which may optionally contain up to 40% by weight of acrylate or methacrylate, in particular methyl methacrylate or n-butyl acrylate. Styrene derivatives must always be present as monomers. The styrene derivative thus contains 100 to 10% by weight, preferably 90 to 20% by weight, particularly preferably 80 to 30% by weight.
present in a proportion of % by weight, and by normal pressure e.g. bulk,
Obtained by solution, suspension or emulsion free radical polymerization, preferably by free radical porous polymerization in water. Suitable graft polymers are prepared by polymerizing the above vinyl monomers of a vinyl monomer mixture in the presence of a rubber having a glass transition temperature of 0°C, preferably 20°C. The graft polymer generally contains 1 to 85% by weight rubber, preferably 10 to 80% by weight. The graft polymers can be grafted in conventional manner in solution, in bulk or in emulsion, preferably in emulsion, the vinyl monomer mixtures being grafted simultaneously or sequentially. Suitable rubbers are preferably diene rubbers and acrylate rubbers. Diene rubbers include, for example, polybutadiene, polyisoprene and copolymers of butadiene with up to 35% by weight of comonomers such as styrene, acrylonitrile, methyl methacrylate and 01-C, alkyl acrylates. The acrylate rubber may contain, for example, optionally up to 15% by weight of other unsaturated monomers such as styrene, methyl methacrylate, butadiene, vinyl methyl ether, acrylonitrile and at least one polyfunctional cross-linking agent such as vinylbenzene, glycol-bis-acrylate, Bisacrylamide, triallyl phosphate, triallyl citrate,
Allyl esters of acrylic acid and methacrylic acid, cross-linked particle type C,-C,alkyl acrylates, especially 0
Emulsion polymers from 2-C, alkyl acrylates, the acrylate rubbers can contain up to 4% by weight of cross-linking comonomers. Mixtures of diene rubbers and acrylate rubbers and rubbers with a core-shell structure are also suitable for producing graft polymers. During graft polymerization, the rubber must be present in separate particles, for example as a latex. These particles generally have an average diameter of 10 to 2.00 On+a. Graft polymerization is carried out by known methods in the presence of rubber latex at temperatures of 50-90°C using a water-soluble initiator such as peroquine disulfate, or by free radical emulsification of the vinyl monomers using a redox initiator. It can be produced by polymerization. Gel content>80% by weight and average particle diameter (aS.)8
Preference is given to emulsion graft polymers prepared by free radical reaction on highly cross-linked rubbers (diene rubbers or acrylate rubbers) of particle type with a diameter of 0 to 800 nm. Technical ABS polymers are particularly suitable. Also suitable are mixtures of vinyl homopolymers and/or copolymers with graft polymers. Other suitable thermoplastics b) are also polyurethanes. These are reaction products of diisocyanates, wholly or mainly aliphatic oligoesters and/or polyesters and/or polyethers, and one or more chain extenders. Thermoplastic polyurethanes are known or can be made by known methods [e.g. U.S. Pat.
No. 11, J. Salanders (SB+1nderS) and C. Frisch, “Polyurethanes, Chemistry and Technology (Polyurethanes, C.
hemistry and technology)J
, Volume ■, pp. 299-451, Interscience Publishing, New York, 1964 and Mobay Chemical Co., Ltd.
bay Che+m1cal Corporation
), A Processing Handbook for Texin, Urethane, and Elastoplastic Materials
ndbook for Tex1n LTrethan
e Elastoplastic Materials
) J, Pittsburgh, FA]. Starting materials for the production of oligoesters and polyesters are, for example, adipic acid, succinic acid, mabesic acid, sebacic acid, oxalic acid, methyladipic acid, glutaric acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid and inphthalic acid. be. Adipic acid is preferred here. Glycols suitable for producing oligoesters and polyesters include, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol,
1.2-Butanediol% 113-Butanediol, l
, 4-butanediol, 2.3-butanediol, 2.
4-butanediol, hexanediol, bishydroxymethylcyclohexane, diethylene glycol and 2
．． 2-dimethylpropylene glycol. Additionally, small amounts of up to 1 mole % of tri- or higher functional alcohols such as trimethylolgloban, chrycerin, hexanetriol may be used together with the glycols. The resulting hydroxyl oligoester or hydroxyl polyester has a molecular weight of at least 600, about 25 to 1
90, preferably about 40-150, a hydroxyl number of about 0.5-2 and a water content of about 0.01-0.2%. Oligoesters or polyesters are also oligomeric or polymeric lactones such as oligo-caprolactone or poly-caprolactone and aliphatic polycarbonates such as poly-1,4-butanediol carbonate or poly-1,6-hexanediol carbonate. Particularly suitable oligo groups which can be used as starting materials for thermoplastic polyurethanes are prepared from adipic acid and glycols having at least one primary hydroxyl group. Polymerization is complete when a rancidity of about 0.5 to 2 lO1 is reached. Thus, the water produced during the reaction can be split at the same time or later,
Therefore, the moisture content at the end is approximately 0. O1-0.05%, preferably 0.01-0.02%. Oligoethers or polyethers for producing polyurethanes are, for example, those based on tetramethylene glycol, propylene gelylcol and ethylene glycol. Polyacetals may also be included and used as polyethers. Oligoether or polyether is 600-2.00
It should have an average molecular weight Mn (number average, measured via the OH number of the product) of 0, preferably l, OOO to 2.000. 4,4'-diphenylmethane diisocyanate is preferably used as the organic diisocyanate for producing polyurethane. These are less than 5% 2.4'
- diphenylmethane-diisocyanate and less than 2% dimer of diphenylmethane-diisocyanate. Furthermore, when calculated as HCQ, the acidity is about 0.005 ~
The content is preferably 0.2%. Acidity, calculated as %HCQ, is determined by extracting the chloride from incyanate in hot aqueous methanol or by hydrolysis with water to release the chloride and titrating the extract with standard silver nitrate solution. Determined by obtaining the concentration of chlorine ions present. Other diisocyanates such as ethylene, ethylidene, propylene,
Butylene, 1,3-cyclopentylene, l,4-cyclohexane, 1,2-cyclohexane, 2,4-tolylene, 2,6-tolylene, p-phenylene, m-phenylene, xylene, 1,4-naphthylene, 1.5-naphthylene, 4,4'-diphenylene diisocyanate, as well as 2,2-diphenylpropane-4,4'-diisocyanate, azobenzene-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, Dichlorohexane methylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, l-chlorobenzene-2,4-diisocyanate, furfuryl diisocyanate, dicyclohexylmethane diisocyanate, inholone diisocyanate, ethylene glycol, butanediol diphenylethane and bis -(isocyanatophenyl)-ether may be used. Organic difunctional compounds which can be used as chain extenders are those containing active hydrogens that react with isocyanates, such as diols, hydroxycarboxylic acids, dicarboxylic acids, diamines and alkanolamines, and water. Examples of these that may be mentioned include ethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol, butanediol, butynediol, xylene glycol,
Amylene gellicol, 1=4-phenylene-bis-β-
Hydroxyethyl ether, 1,3-phenylene-bis-β-hydroxyethyl ether, bis-(hydroxymethylcyclohexane), hexanediol, adipic acid, ω-hydroxycaproic acid, thiodiglycol, ethylenediamine, propylenediamine, butylenediamine, Hexamethylenediamine, cyclohexylenediamine, phenylenediamine, tricynediamine, xylylenediamine, diaminodicyclohexylmethane, inphoronediamine, 3,3'-dichlorobenxidine 3
, 3' (nitrogenzidine, ethanolamine,
Aminopropyl alcohol methylpropanolamine, 2-aminocyclohexyl alcohol and p-aminobenzyl alcohol. The molar ratio of oligoester or polyester to difunctional chain extender is from 1:1 to 1:50, preferably 1:50.
2-1:30. In addition to the difunctional chain extender, tri- or more functional chain extenders may also be used in amounts as low as about 5 mole percent based on the number of moles of the difunctional chain extender. obtain. Tri- or more-functional chain extenders of this type include, for example, glycerin, trimethylolpropane, hexanetriol, pentaerythritol and triethanolamine. Also, functional components such as butanol may be used to produce thermoplastic polyurethanes. Diisocyanates, oligoesters, polyesters, polyethers,
Chair extenders and -functional components are known in the literature or can be obtained by methods known in the literature. The known preparation of polyurethanes can be carried out, for example, as follows: Thus, for example, oligoesters or polyesters, organic diisocyanates and chain extenders are preferably added to about 50%
Heat to a temperature of ~220°C and then mix. The oligoester or polyester is preferably first heated individually, then mixed with the chair extender, and the resulting mixture is mixed with the preheated isocyanate. The mixing of the starting components for producing the polyurethane can be carried out using a mechanical stirrer which is capable of stirring vigorously within a short time. If the viscosity of the mixture is also to rise very quickly before stirring, the temperature should be lowered or a small amount (0.001-0.05
% (by weight, based on ester) of citric acid or the like to either reduce the rate of reaction. To increase the reaction rate, U.S. Patent No. 2.729
．． Suitable catalysts such as those listed in No. 618 may be used, such as tertiary amines. Suitable elastomers b3) for component b) for preparing the mixtures of the invention are the polyurethanes mentioned above, styrene, partially hydrated butadiene block copolymers (for example KraLon from Shell), as long as they are inherently elastic. G
@), the rubbers listed above for graft polymers,
As long as it is elastic, it is the graft polymer itself and the elastic polycarbonate-polyether block copolymer. Elastomers are known. Mixtures of polycarbonates a) and elastomers b) according to the invention can be prepared, for example, by mixing components a) and b3) as a melt in conventional equipment, such as kneaders, single- or multi-wave extruders or rollers. Furthermore, the object of German patent application No. P3.833,953゜6 is to melt polycarbonate a) and produce elastomer b3.
) and homogenized in the polycarbonate melt, from 0°1 to 99.9% by weight, preferably from 1 to 98% by weight, in particular from 2.5 to 90% by weight of polycarbonate a ) and 99.9 to 0.1% by weight, preferably 99 to 2% by weight, especially 97.5 to 10% by weight of elastomer b3). Mixtures of polycarbonate a) according to the invention and other thermoplastics bl) or b2) are for example components a) and b)
or by mixing the components on a kneader, roller or single or multi-wave extruder. The object of German Patent Application No. P 3.833,953.6 is either to mix all the components as a solution and to process this mixture in a conventional manner, or to mix all the components in the molten state and to obtain a homogeneous solution. 0.
1 to 99.9% by weight, preferably 1 to 98% by weight, especially 2.5 to 90% by weight of polycarbonate) a) and 99.9%
~0.1% by weight, preferably 99-2% by weight, especially 97% by weight
．． 5 to 10% by weight of other thermoplastics bl) or b
2). Also additives customary in component b), such as fillers and/or
Alternatively, nucleating agents and/or fibers can be added in customary amounts to the mixture according to the invention as component C). Inorganic fillers include, for example, ceramic fillers such as aluminum nitrate, silicates, titanium dioxide, talc, chalk, limestone, soot, fibers, graphite and, for example, glass, carbon or liquid crystalline polymers. The nucleating agent can be, for example, barium sulfate or Ti01. These additives can be mixed in customary amounts either with component b) before the preparation of the mixture according to the invention or with the polycarbonate of component a) or subsequently with the polycarbonate according to the invention. may be processed in a mixture of components a) and b). Likewise, the additives mentioned can be added in customary amounts to the polycarbonate of component a) before, during or after mixing with component b). The mixtures according to the invention can be processed in conventional manner on conventional machines into various shaped bodies. The mixtures of the invention and the moldings produced therefrom can be used, for example, in the automotive and electronics industry for producing bumpers and housings. Example C) gt min CI) Corresponding to Example Bl) C2) Polystyrene produced by free radical polymerization of styrene in a known manner. My (measured by light scattering) 260,
000°C3) 1.289 Relative viscosity '7-+ (CHxc Q
Bisphenol A polycarbonate having a temperature of 25°C and C-0,51/dQ). C4) Polymethyl methacrylate C3) Polycaprolactam with a relative viscosity of 3.0 (measured as a 0.5% by weight solution in m-cresol) C6) Polyethylene terephthalate D) Mixture DI) Substance CI) 37j and Substance C2) 377 Each was dissolved in 200ml of methylene chloride. The solutions were then combined and the solvent was partially removed under vacuum until the solution thickened, from which sheets with a thickness of 200/Jll were produced on film stretching pliers. 6 pieces of this sheet were stacked and heated in air at a pressure of 270 bar.
A rectangular compact having a thickness of 1-042+a+s was produced by compacting for 5 minutes at . C2) Substance CI) 30F and substance C3) 301 were each dissolved in 200-methylene chloride. Then combine the solutions and
The solution was thickened as in Example DI) and to a thickness of 210
A μ■ sheet was produced. Six pieces of sheets were stacked as in Example DI) and compressed in air at a pressure of 210 bar for 5 minutes at 250° C. to yield 0.98! A rectangular shaped body with a thickness of lJo+m was produced. C3) Substance CI) 25jl and substance C4) 251 were each dissolved in 200 methylene chloride. The solutions are then combined and the solvent is partially removed in vacuo until the solution thickens;
A sheet having a thickness of 2,007,711 mm was then produced from this on a film stretching bench. 6 of this sheet
Stack the pieces and heat in air at a pressure of 200 bar, 2
Compression at 70° C. for 5 minutes produced a rectangular compact with a thickness of 0.61 mm. C4) Substance C3) 702 was melted together with substance CI) 301 in a flask and homogenized. After cooling the melt, the mixture was milled and the particles were compressed to form Example C3.
) A molded body having a thickness of 1°61111 was produced as described in . C5) Substances C6) 35y and CI) 15y were compressed to produce a molded body with a thickness of 1.6-- as described in Example C4). E) Testing of Samples Produced by D Messer
s, Brabender, Type 80230
Measurements were made using a torsion spindle manufactured by /. The samples were introduced at the following temperatures with a heating rate of IK/min and the samples were subjected to a tensile force of 10 p during the time for all measurements. Torque is 1.5
70 gcm". Since the sample did not have sufficient internal force above this, the deformation of the sample was clearly detected at a modulus value below lOMpa. Results: The shear modulus of the example, Mpa T-50 °C T-160”o = 200’c substance
C2) 1. OQO<10 <10 substances c3
) 950 <10 <10 substances C4
) 980 <10 <10 substances C5
) 400 120 70 substances GO)
800 50 40DI)
1.000 80 65D2)
950 230 57D3) 1
．． 050 20D4) 1,000
200 40D5) 950
180 80 Sheets from mixtures of special new polycarbonates a) and other thermoplastic polycarbonates bl) are described in German Patent Application No. 3.840.166.5
(LeA 26.543), at which time b
The weight ratio of a) to l) is 0.1:99.9-99.
9:0.1% by weight, preferably 5:95 to 95:5% by weight, especially 10:90 to 90:10% by weight. German patent application no. p3.833,953.6 (Le
A 26.397) 0, 1: 99.
Difunctional polycarbonates mixed with suitable other thermoplastic polycarbonates with component bl) containing only difunctional carbonate structural units (■a) in a mixing range of 9% by weight to 99.9:0.1% by weight. carbonate structural unit (Ia
) and optionally (■a) The polycarbonates of component a) of the patent application are obtained by rawhide transparent mixtures which are particularly suitable for optical applications, in particular in the production of optical data storage media such as compact discs. It was shown that That is, the transparency is determined in each case by the bifunctional structural unit (Ia)
+0.0 based on the total molar amount of 100 mol% of (■a).
1 mol% (Ia): 55% mol% (Ia) and 65 mol%
(Ia):99.9 mol % (Ia) of bifunctional structural units (Ia):(■a), where this is shown to occur on polycarbonate components a) and b). It does not depend on the distribution of structural units (Ia) and (■a) in . The production of compact discs from thermoplastic mixtures is known. (For example, German Patent Application Publication No. 3.
704.688). Thus, the ninth feature of the present invention is 0.1 to 99.9 fr amount% of bifunctional carbonate structural units (Ia) and optionally (■a)
German patent application no. P3,833.953.
No. 6 component a) polycarbonate and 99.9-0.
German patent application No. P3,833,953.6 containing only 1% by weight of difunctional carbonate structural units (■a)
the use of mixtures of other thermoplastic polycarbonates according to component bl) of the No. % is in each case 100% by weight and the molar ratio of structural units (Ia) to structural units (■a) is in each case the structural units () in the mixture of polycarbonate components a) and bl).
0.1 mol% (Ia) to 55 mol% (Ia) and 6 based on the total molar amount of 100 mol% of Ia)+(■a)
5 mol% (Ia) to 99.9 mol% (Ia), preferably 0.5 mol% (Ia) to 50 mol% (Ia)
and 70 mol% (Ia)"99-9 mol% (Ia), especially 1 mol% (Ia) to 45 mol% (Ia) and 80 mol% (Ia) = 99-9 mol% (Ia) Thus, the molar amount of the structural unit (■a) is in each case (Ia
)+(■a) in amounts complementary to (Ia) in each case, based on 100 mol % of (a). In addition, the object of the present invention is products for optical applications, in particular data storage media, very in particular compact discs, which are produced in whole or in part from the abovementioned polycarbonate mixtures which can be used according to the invention. The polycarbonate of component a) is from the diphenols (I) of German Patent Application No. P 3.833,953.6, optionally mixed with the diphenols (■) of that patent application. The thermoplastic polycarbonates of other components bl) of German patent application No. P3.833,953.6 are, as already mentioned, those based on diphenols (■) of that patent application, preferably (■b). In the formula, n represents 0 or l, Y is a single bond, C, -C,. Alkylene%C, ~C3゜Alkylidene, C, #C,, Cycloalkylene, C, ~C
, cycloalkylidene, -〇--S --5O--S
O! - or -CO-; and R independently represents H, CH,, Ca or bromine. A suitable diphenol (■b) is described in German patent application no.
．． This has already been mentioned in connection with the general formula (■) of No. 833,953.6. Suitable diphenols (■b) are especially bisphenol z1
Bisphenol-A and tetramethylbisphenol-
Preferred diphenols for producing polycarbonate component a) A are those described in German Patent Application No. 3,833.953.6.
Diphenols (II) and (III) of No. Suitable polycarbonate mixtures a)+b) are mixtures of the particularly preferred diphenol-based polycarbonates mentioned above. The polycarbonates of components a)+b) which can be used according to the invention can be linear or branched independently of one another. In principle, the molecular weights of the individual components can be varied within wide limits. The molecular weight My (weight average, determined by gel permeation chromatography) of the polycarbonate used is preferably from 10.000 to 190.0 OOj'1 for component a).
mol, and for component b) 12,000-130
．． 0OOj is 1 mole. Also, molecular non-uniformity Un-My/Mn-1 (Mn-number average molecular weight, measured by gel permeation chromatography)
can in principle vary within a wide range. These mixtures are preferably such that Un for at least one of components a) or b) is less than 2, preferably less than 1.3, especially 0.9
It is smaller. Components a) and b) have molecular non-uniformity Un
It has been found to be particularly advantageous if -Mw/Mn-1 is less than 2 for both components. The ratio of diphenols (I), in particular (I[) and/or (m), for producing polycarbonate component a) is 0, based on the specific total amount of diphenols used for producing polycarbonate component a). .1-100 mol % and depends on the conditions according to the invention regarding the structural units (Ia) and (■a). On the basis of this condition according to the invention, the expert is left to decide how to adjust the weight ratio depending on the molar ratio of bisphenols used within the particular polycarbonate a) or b). For example, it is advantageous to use particularly high molar proportions of bisphenol (I) for producing polycarbonate a). In this case, up to 40% by weight of this polycarbonate)
Particular preference is given to using either a) or more than 80% by weight of this polycarbonate. To produce polycarbonate components a) and b),
When only bisphenol-21 bisphenol-a and tetramethylbisphenol-A are combined with diphenol (■), especially diphenol (n), only a very small mol % of diphenol (1) and polycarbonate a)
It may then be advantageous to use component a) in high degrees by weight. Generally, the conditions described above, e.g. about 10 to 55 mole % diphenol (I)
, in particular polycarbonate a) having a molar ratio of (n) of at least 0
It can be mixed with 0% by weight, preferably more than 30% by weight of polycarbonate) b). In addition to their transparency, the polycarbonate mixtures described above which are suitable for optical applications have particularly high thermal dimensional stability. In this regard, the polymer mixture has a cloudiness index (ASTM D) of less than 10% for samples of at least 200 μm
1003)) is transparent. The preparation of the polycarbonate mixtures according to the invention suitable for optical applications can be carried out in customary mixing equipment at temperatures of 250 to 400° C. or by combining the polycarbonate components a) and b).
The polycarbonate mixture can be prepared for optical applications by using a solution of the polycarbonate in a suitable solvent such as CH, (1) and then removing the solvent by evaporation. The processing into shaped bodies for optical systems or optical applications is carried out in known manner. Shaped bodies suitable for optical applications are, for example, discs, plates, wires, fibers and other three-dimensional components. Uses are in the automotive industry, co-bined vision and protective screens, cover plates for electrical display devices, signal lights, signs and traffic signs, lenses for photographic and film cameras, photoconductors in the form of fibers and cables and of course data. It is understood that use as a storage medium, in particular as a compact disc, is meant. Additives customary for optical applications, such as in particular dyes, UV absorbers, heat stabilizers and H, O, are present in customary amounts. It may be advantageous to add them to the mixtures used according to the invention.An object of the invention is thus also the use in optical systems of polycarbonate mixtures of the invention containing additives customary for optical applications.Also an object of the invention is a difunctional carbonate structural unit (I
polycarbonates of component a) of German patent application no. German patent application no. P3.8
33,953.6, wherein component a
) is present in an amount of 1O11 to 89.911% by weight, and the other component bl) polycarbonate is present in an amount of 89.9 to 10% by weight.
1% by weight, where the sum of a)+bl) is in each case 100% by weight, and in each case structural units (I ) + Based on the total molar amount of 100 mol% of (■a), the molar ratio of (Ia) to the structural unit (■a) is 0.1 mol% (I a) to 55 mol% (Ia) and 65 mol% (Ia) to 99.9 mol% (Ia), preferably 0.5 mol% (Ia) to 50 mol% (Ia) and 70 mol% (Ia) to 99.9 mol% (Ia), In particular 1 mol% (Ia) to 45 mol% (Ia) and 80 mol% (Ia) to 99.9 mol% (Ia) and 50% by weight (Ia) to 50% by weight (■a ) weight%
are excluded. Furthermore, in these polycarbonate mixtures according to the invention, German patent application no.
Poly(meth)acrylates with grafted polycarbonate chains according to No. 3.911,222.5 (La A26.692) are excluded. Example D A) Diphenols German patent application no. P3.83
The diphenol (II) of Example A of No. 3,953.6 (page 12 of this patent application) was used. B) Preparation of copolycarbonate 8.6 2.2-Bis-(4-hydroxyphenyl)-propane 148.2j (0.65 mol), Example a of German Patent Application No. P3.833,953.6 of diphenol 108.59 (0.35 mol), KOH 236.1 (
6 mol) and 2.7002 ml of water were dissolved with stirring under an inert gas atmosphere. A solution of 8.862 mm of inoctylphenol in 2.500 mm of methylene chloride was then added. Phosgene 1981 (2 mol) at pH 13-14 and 2
The mixture was introduced into a well-stirred solution at 1-25°C. Ethylpiperidine l- was then added and the mixture was stirred for a further 45 minutes. Separate the aqueous phase that does not contain bisferrate,
After being partially acidified with phosphoric acid, the organic phase was washed with water until neutral and the solvent was removed. The polycarbonate exhibited a relative viscosity of 1.20 (?r** determined against a solution of 0.5% by weight (7) HolJ carbonate in CH, CQ) and a Tgl of 85°C. Freezing or glass transition temperatures were measured using differential scanning calorimetry (DSC). Preparation of polycarbonate B7 The preparation of B7 corresponds to the preparation of B,1, using inoctylphenol in an amount of 1.0 mol % as chain terminator. The obtained particles have η1. . 1.30 and 7g at 237°C, both silvers being determined in the manner described above for B6. 2.2-bis-(4-hydroxyphenyl)-propane 102.62 (45 mol %) and diphenol 170.52 (55 mol %) of Example A of German Patent Application No. P 3.833,953.6 ) and 4.749 moles of inoctylphenol and 2 moles of phosgene as chain terminators, the preparation of B8 was carried out as described above for B6. The resulting particles had an η1.1 of 1.29 and a Tg of 204°C.
and both values were determined as above for B6. Preparation of Polycarbonate B9 Also 2,2-bis-(4-hydroxyphenol)-propane 182.47 (80 mol %) and diphenol 622 (of Example A of German Patent Application No. P3.833,953.6) 20 mol%) and inoctylphenol 6.18I (0,03
The preparation of B9 was carried out analogously to 86 above using mol) and phosgene. The resulting particles had a 1,1 of 1.30 and a Tg of 173°C, both values measured as above for B6. C0 component CI)-86 C2) is the value stated for B6 η, , 1.
2,2-bis-(4-
It is a homopolycarbonate of hydroxyphenyl)-zolopane. C3)-87 C4)-88 C5)-B9 C6) also has an η10. of 1,28 measured as described for B6. and a Tg of 148°C, where Mw=28.200 and Mn-14,100 2
, 2-bis-(4-hydroxyphenyl)-propane homopolycarbonate. C7) Corresponds to C6) but with a non-uniformity of 0.89. C8) is η10 of 1.29 as explained for C6
．． A homopolycarbonate of 2,2-bis-(4-hydroxyphenyl)-propane with an 'rg of 197°C. D Mixtures Dt) Cl 50m and C250m were homogenized in the molten state at 320° C. on an r-type extruder. Diameter 1
A compact disc with a diameter of 2 cm+ was obtained from the resulting sample by injection molding in a NeLsal injection molding machine (solid temperature 350-360° C.). The double refraction was measured in the axial direction on the compact disc. Double refraction is measured using a polarizing microscope using a normal comparator (
The evaluation was performed using optical path difference measurement using Compact discs were manually evaluated for transparency. The glass transition temperature of the sample to be examined was determined from the already mentioned DSCJ: optical path difference (nIl/-)+@; Tgl 64°C, presence of transparency. D2) 90 wt% C4 and 10 wt% C7D3)
75 tt C4tp 25 〃C6D4
) 80 // C3 // 20 tt
C6D5) 70 tt C4tt
30 〃C6D6) 80 tt C5/
/ 20 〃C6D7) 70 tt
C3// 30/l C6D8)
50 // C3tt 50 tt
C3D9) 80 tt C3//2
0 tt C8 mixtures D2) to D9) are mixed,
Mote Messrs. Granulation was carried out in a known manner on a two-way extruder ZSK32 from Werner and Pflaiderer at a temperature of 300-330°C. Next, the cloudiness index was measured using ASTM on a 0.2n-thick sample.
D 1003 and transparency was evaluated in all cases. The main features and aspects of the invention are as follows. 1, a) R1 of formula (Ia) in an amount of 100 to 2 mol %, based on the total molar amount of difunctional carbonate structural units.
and R1 are independently hydrogen, halogen, C0-C, alkyl, C1-C, cycloalkyl, C, -C8°aryl or C7-CI! represents aralkyl; m represents an integer from 4 to 7; Rs and R4, individually selected for each X, independently represent hydrogen or C1-C, alkyl; and X represents a carbon atom; R3 and R4 both represent alkyl on at least one Xi atom: a difunctional carbonate structural unit corresponding to and an amount of other difunctional carbonate structural units (■a) up to 100 mol % in the formula , -2- represents an aromatic group having 6 to 30 carbon atoms;
99.9% by weight; b) characterized by containing only difunctional carbonate structural units corresponding to formula (■a) and at least one thermoplastic polycarbonate other than component (a)) 99.
9 to 0.1% by weight, and optionally C) additives customary for optical applications, the sum of the weight percentages of a) and b') being in each case 100 mol%, and the structure unit(
■ The molar ratio of structural units (Ia) to a) is in each case 0 based on the total molar amount of structural units (I a) + (■a) 100 mol % in the mixture of polycarbonate components a) + b). .1 (I a) to 55 mol% (I
a) and 65 (I a) to 99.9 mol % (Ia) for optical applications. 2. In each case, the molar ratio of structural unit (Ia) to structural unit (■a) is 100
0.5 to 50 mol % and 70 (Ia) to 99.9 mol % (Ia) based on the total mole amount of mol %,
The product described in item 1 above. 3. The molar ratio of (Ia) to (■a) is in each case 1 (Ia) to 45 mol% (Ia) based on the total molar amount of structural units (Ia) + (■a) 100 mol% and 80
(Ia) to 99.9 mol% (Ia). 4.a) R' in the formula (Ia) in an amount of 100 to 2 mol %, based on the total molar amount of difunctional carbonate structural units;
and R8 are independently hydrogen, halogen, C, -Ca alkyl, C1-C, cycloalkyl, C6-C16 aryl or C7-C1! represents aralkyl; m represents an integer from 4 to 7; R3 and R6, individually selected for each X, independently represent hydrogen or C, -C, alkyl; and X represents a carbon atom; Rs and R4 together represent alkyl on at least one x atom; and up to 100 mol % of other difunctional carbonate structural units (■a), where -2- represents 6 carbon atoms; Thermoplastic, aromatic polycarbonate resin having a weight average molecular weight of at least 10,000 representing from about 0.1 to 30 aromatic groups;
99.9% by weight: b) at least one thermoplastic polycarbonate other than component (a), characterized by containing only difunctional carbonate structural units corresponding to formula (■a) 99.9
~0.1% by weight and optionally C) additives customary for optical applications, the sum of the weight% of a) and b) being in each case 100 mol% and the structural units ( ■a
The molar ratio of structural units (Ia) to ) is in each case 0.1, based on the total molar amount of structural units (Ia) + (■a) 100 mol % in the mixture of polycarbonate components a) and b). (Ia) ~ 55 mol% (Ia) and 65
(Ia) - 99.9 mol % (Ia) of a bottom-forming composition. 5. Optical data storage medium as a product according to item 1 above. 6. A compact disc as the medium described in 5 above. 7. A product manufactured by the method described in 4 above. 8. An optical data storage medium manufactured by the method described in 4 above. 9. A compact disc manufactured by the method described in 4 above. 10, a) Component a) 10.1 to 89.9 as described in 1 above
% by weight, and b) the components described in item 1 above b) 89.9 to 1 O, 1% by weight, in which case the sum of a) + b) is 100% by weight
and the molar ratio of (Ia) to (■a) corresponds to that described in 1 above, in which case 50% by weight (Ia):5
Polycarbonate mixtures excluding a weight ratio of 0% by weight (■a) and excluding pol(meth)acrylates with grafted polycarbonate chains as polycarbonate component a) or b).

Claims (1)

[Claims] 1. a) Formula (I a) ▲ Formula in an amount of 100 to 2 mol % based on the total molar amount of difunctional carbonate structural units,
There are chemical formulas, tables, etc. ▼ (I a) In the formula, R^1 and R^2 independently represent hydrogen, halogen, C
_1-C_3 alkyl, C_5-C_6 cycloalkyl, C_6-C_1_0 aryl or C_7-C_1_
2 represents aralkyl; m represents an integer of 4 to 7; R^3 and R^4 individually selected for each X independently represent hydrogen or C_1 to C_6 alkyl;
and X represents a carbon atom; R^3 and R^4 both represent alkyl on at least one X atom; difunctional carbonate structural units corresponding to and other amounts up to 100 mol %; Difunctional carbonate structural unit (VIIIa) ▲Mathematical formula, chemical formula, table, etc.▼(VIIIa) In the formula, -Z- represents an aromatic group having 6 to 30 carbon atoms; A thermoplastic, aromatic polycarbonate resin having a weight average molecular weight of about 0.1 to
99.9% by weight; b) component (a) characterized by containing only difunctional carbonate structural units corresponding to formula (VIIIa);
) at least one thermoplastic polycarbonate other than 9
9.9-0.1% by weight and optionally c) additives customary for optical applications, the sum of the weight-% of a) and b) being in each case 100 mol%, and The molar ratio of structural units (I a) to structural units (VIIIa) is in each case based on the total molar amount of 100 mol % of structural units (I a) + (VIIIa) in the mixture of polycarbonate components a) + b). as 0.1 (I a) to 55 mol% (
Ia) and 65 (Ia) to 99.9 mol% (Ia)
products for optical applications. 2. A compact disc as a medium according to claim 1. 3. A compact disc manufactured from the product according to claim 1.